The topology of amorphous materials can be affected by mechanical forces during compression or milling, which can induce material densification. Here, we show that densified amorphous silica (SiO 2 ) fabricated by cold compression of siliceous zeolite (SZ) is permanently densified, unlike densified glassy SiO 2 (GS) fabricated by cold compression although the X-ray diffraction data and density of the former are identical to those of the latter. Moreover, the topology of the densified amorphous SiO 2 fabricated from SZ retains that of crystalline SZ, whereas the densified GS relaxes to pristine GS after thermal annealing. These results indicate that it is possible to design new functional amorphous materials by tuning the topology of the initial zeolitic crystalline phases.

The negative thermal expansion material potassium cadmium dicyanoargentate, KCd[Ag(CN)2]3, is studied at high pressure using a combination of X-ray single-crystal diffraction, X-ray powder diffraction, infrared and Raman spectroscopy, and density functional theory calculations. In common with the isostructural manganese analogue, KMn[Ag(CN)2]3, this material is shown to exhibit very strong negative linear compressibility (NLC) in the crystallographic c direction due to structure hinging. We find increased structural flexibility results in enhanced NLC and NTE properties, but this also leads to two pressure-induced phase transitions-to very large unit cells involving octahedral tilting and shearing of the structure-below 2 GPa. The presence of potassium cations has an important effect on the mechanical and thermodynamic properties of this family, while the chemical versatility demonstrated here is of considerable interest to tune unusual mechanical properties for application.

The Raman modes of α-quartz-type boron phosphate were found to be extremely stable in frequency over a large temperature range from 300–1000 K. In order to determine the origin of this behavior, the material was also studied at high pressure up to 6 GPa. Upon compression, a classical behavior was observed with mode Grüneisen parameters ranging from −0.08(2) to 3.0(1). The present results indicate that the high temperature behavior in this material is an example of an unusual compensation effect between phonon–phonon interactions and implicit contributions due to thermal expansion. Phonon stability is of utmost importance for materials properties that are dependent on it such as dielectric and piezoelectric properties, for example. Boron phosphate belongs to the important class of α-quartz-type piezoelectric materials for which temperature stability is of primordial importance for resonator and sensor applications.

In this paper, we present the different characterization techniques used to measure the mechanical properties of silica aerogels. The mechanical behavior of aerogels is generally described in terms of elastic and fragile materials (such as glasses or ceramics) but also in terms of plastic media in compression testing. Because of these very different mechanical behaviors, several types of characterization techniques are proposed in the literature. We first describe the dynamic characterization techniques such as ultrasounds, Brillouin scattering, dynamic mechanical analysis (DMA) to measure the elastic properties: Young’s modulus ( E ), shear modulus ( G ), Poisson ratio ( υ ) but also attenuation and internal friction. Thanks to "static" techniques such as three-point bending, uniaxial compression, compression we also access to the elastic modulus ( E ) and to the rupture strength ( σ ). The experimental results show that the values of the elastic and fracture moduli measured are several orders of magnitude lower than those of a material without porosity are. With regard to the brittleness characteristics, Weibull's analysis is used to show the statistical nature of the fracture resistance. We also present the SENB (Single Edge Notched Beam) technique to characterize toughness ( K IC ) and the stress corrosion mechanisms, which are studied in ambient conditions and temperature by the double cleavage drilled compression experiment (DCDC). In the last part of the paper, we show how, during the isostatic compression test, aerogels behave like plastic materials. The data allow calculating the bulk modulus ( K ), the amplitude of the plastic deformation and the yield strength ( σ el ), which is the boundary between the elastic and plastic domains. These different techniques allow understanding which parameters influence the overall mechanical behavior of aerogels, such as pore volume, but also pore size, internal connectivity and silanol bounds content. It is shown that the pore size plays a very important role; pores can be considered as flaws in the terms of fracture mechanics.

alpha-Quartz-type gallium phosphate and representative compositions in the AlPO4-GaPO4 solid solution were studied by x-ray powder diffraction and absorption spectroscopy, Raman scattering, and by first-principles calculations up to pressures of close to 30 GPa. A phase transition to a metastable orthorhombic high-pressure phase along with some of the stable orthorhombic Cmcm CrVO4-type material is found to occur beginning at 9 GPa at 320 degrees C in GaPO4. In the case of the AlPO4-GaPO4 solid solution at room temperature, only the metastable orthorhombic phase was obtained above 10 GPa. The possible crystal structures of the high-pressure forms of GaPO4 were predicted from first-principles calculations and the evolutionary algorithm USPEX. A predicted orthorhombic structure with a Pmn2(1) space group with the gallium in sixfold and phosphorus in fourfold coordination was found to be in the best agreement with the combined experimental data from x-ray diffraction and absorption and Raman spectroscopy. This method is found to very powerful to better understand competition between different phase transition pathways at high pressure.

AlPO4-17, known as the oxide with the highest negative thermal expansion (NTE), was studied under high pressure by angle-dispersive X-ray diffraction (XRD), mid- and far-infrared (IR) spectroscopy. Upon increasing pressure, the closure of the (P-O-Al) angle destabilizes the porous AlPO4-17 structure, which drives the amorphization process. On the basis of the decrease in intensity of the XRD lines and broadening of the IR modes, the material was found to begin to amorphize near 1 GPa. XRD, mid- and far-IR analysis evidenced pressure-induced framework softening and complete irreversible amorphization near 2.5 GPa corresponding to the collapse of the pores. The bulk modulus and its first pressure derivative (B-0 = 31.2(5) GPa and B'(0) = -10.1(3)) at ambient temperature were determined by fitting a third order Birch-Murnaghan equation of state (EOS) to the pressure-volume data. The material is extremely compressible and exhibits an elastic instability. Anomalous (negative) values of B'(0) are very rare and have been observed previously for cyanides and metal-organic frameworks. Such an instability appears to be characteristic of materials, which exhibit strong NTE behavior and indicates a link between NTE and anomalous compressibility behavior. Mid-IR, far-IR, nuclear magnetic resonance, and pair distribution function analysis of the new amorphous form allow an amorphization mechanism to be proposed corresponding to a collapse of the structure around its pores retaining the columns built up of cancrinite cages and hexagonal prisms, based on alternating AlO4 and PO4 tetrahedra. An increase in coordination number of 10% of the Al atoms was observed. The pressure-induced amorphization in the strong NTE material AlPO4-17 opens the door to the development of new technological applications as crystal-amorphous nanocomposites with zero or specifically selected thermal expansion coefficients.

Microporous AlPO4-54, which exhibits the largest pores among zeolites and aluminophosphates with a diameter of 12.7 A, was investigated at high pressure by X-ray powder diffraction (XRD), mid- and far-infrared (IR) spectroscopy in diamond anvil cells. The material undergoes a phase transition beginning around 0.8 GPa. The amount of AlPO4-8 gradually increases with pressure and the phase transition is complete between 2 and 3 GPa. The closure of the (P—O—Al) angle destabilizes the structure of AlPO4-54, which drives the transition to AlPO4-8. The pressure-induced phase transformation of AlPO4-54 to AlPO4-8 is associated with a symmetry reduction from hexagonal to orthorhombic and with a change in the unidirectional ring channel parallel to the c-axes from 18 to 14 AlO4 and PO4 tetrahedra. An abrupt decrease along the b direction is linked to the formation of 4 new rings of 6 tetrahedra with significant structural reorganization. The transition is followed by irreversible amorphization beginning around 3.5 ...

The results obtained by high pressure neutron powder diffraction and single-crystal x-ray diffraction for the P4mm-Pm (3) over barm phase transition in the prototype ferroelectric perovskite lead titanate are shown. Neutron diffraction is found to be strongly sensitive to the dipolar moment in the PbTiO3 unit cell due to the gradual reduction of the displacement of the Ti and O atoms from centrosymmetric positions in the cubic perovskite structure which exhibits anti-phase scattering of Pb, Ti and O atoms. From applying both techniques, the anomalously high Debye-Waller factor for the lead atoms confirms the disordered character of the cubic phase. High pressure single crystal x-ray diffraction also perfectly describes the ferroelectricparaelectric transition and will be the technique of choice to solve higher pressure structures for PbTiO3.

Gallium arsenate (GaAsO4) has the highest piezoelectric properties among alpha-quartz-type materials. We describe first-principles calculations of the linear and second-order nonlinear optical properties of GaAsO4 combined with measurements of its second harmonic generation (SHG). Our calculations show that GaAsO4 has a SHG efficiency between 7.1 (LDA) and 12.3 pm/V (GGA), which is in agreement with our experiments (7.5 +/- 1.5 pm/V) using the technique of Maker fringes. This SHG efficiency, attributed to an electronic transition from O 2p to As 4 s states, is higher than that observed in GaPO4 due to a better polarizability of As atoms. Thus, the thermal stability of GaAsO4 (no phase transition up to its thermal decomposition at 1303 K) associated with its high laser damage threshold (0.93 GW/cm(2)) make this compound a promising bifunctional material for piezoelectric and nonlinear optical applications at high temperatures.

Extreme conditions change the behavior and reactivity of elements and compounds and permit the synthesis of novel materials. In the case of group IV oxides, molecular CO 2 and a network solid silica, which were considered to be incompatible, are found to react under HP-HT conditions. A crystalline CO 2 -SiO 2 solid solution was synthesized from molecular CO 2 and microporous silicalite SiO 2 at 16-22 GPa and temperatures above 4000 K in a laser heated diamond anvil cell [1]. Synchrotron X-ray diffraction data show that the crystal adopts a densely packed α-cristobalite structure (space group P4 1 2 1 2) with carbon and silicon in 4-fold coordination. This occurs at pressures at which SiO 2 normally adopts a 6-fold coordinated rutile-type stishovite structure. The P-T conditions used in this study represent a compromise between the respective stabilities of 3- and 4-fold coordination in CO 2 and 4- and 6-fold coordination in SiO 2 . This solid solution can be recovered at ambient pressure at which the unit cell volume is 26% lower than that of α-cristobalite SiO 2 . This is due to the incorporation of much smaller carbon atoms, resulting in the collapse of the oxygen sublattice. The unit cell volume and the different C and Si sites identified in Raman spectroscopy are consistent with a C:Si ratio of 6(1):4(1). The tetragonal c/a ratio increases from 1.283 at 16 GPa to 1.303 at ambient pressure and is lower than that of SiO 2 due to the more compact structure of the new material and essentially corresponds to that of the dense rutile-type oxygen sublattice. This can explain the small variation in volume observed for this phase corresponding to a bulk modulus of about 240 GPa. Due to the incorporation of silicon atoms, this hard solid based on CO 4 tetrahedra can be retained as a metastable phase. This strongly modifies standard oxide chemistry and shows that carbon can enter silica giving rise to a new class of hard, light, carbon-rich oxide materials with novel physical properties.

The authors therefore wish to retract this Article due to content related concerns.

Extreme conditions permit unique materials to be synthesized and can significantly update our view of the periodic table. In the case of group IV elements, carbon was always considered to be distinct with respect to its heavier homologues in forming oxides. Here we report the synthesis of a crystalline CO 2 –SiO 2 solid solution by reacting carbon dioxide and silica in a laser-heated diamond anvil cell ( P =16–22 GPa, T >4,000 K), showing that carbon enters silica. Remarkably, this material is recovered to ambient conditions. X-ray diffraction shows that the crystal adopts a densely packed α-cristobalite structure ( P 4 1 2 1 2) with carbon and silicon in fourfold coordination to oxygen at pressures where silica normally adopts a sixfold coordinated rutile-type stishovite structure. An average formula of C 0.6(1) Si 0.4(1) O 2 is consistent with X-ray diffraction and Raman spectroscopy results. These findings may modify our view on oxide chemistry, which is of great interest for materials science, as well as Earth and planetary sciences.

GaAsO4 crystals were grown by a hydrothermal epitaxial process. Microcrystalline GaAsO4 powder was first synthesized by hydrothermal methods by using GaAs as a starting material in a sulfuric acid solvent under oxidizing conditions. Experimental conditions were optimized and the yield of the nutrient synthesis reached 88%. GaAsO4 powder was then used as the nutrient for growing GaAsO4 single crystals by epitaxy on (21¯0) oriented GaPO4, AlPO4 and GaAsO4 plates. Crystal growth was performed in a horizontal PTFE-lined autoclave divided into two parts using sulfuric acid as the solvent under a slow heating gradient. Hydrothermal conditions were optimized in order to improve the crystal quality. The influence of the nature and orientation of the seeds on the growth rate was studied. From the solubility curve, the solute supply ΔS as a function of temperature during the growth process was calculated. Transparent crystals were obtained with ΔS between 0.002 and 0.009mol/L. Large crystals (3.9×1.8×1.4cm3) of gallium arsenate were obtained. These crystals were cut into (21¯0), (010) and (001) plates. Mapping using Raman spectroscopy was performed in order to study the growth recovery on the seed. GaAsO4 crystals were characterized by infrared spectroscopy in order to quantify the amount of OH groups in the crystal structure. A low value of the absorption coefficient α at 3300cm−1 was measured 0.067cm−1 indicating a good crystal quality. Optical measurements were performed on GaAsO4 crystals by UV–vis–NIR spectrophotometry. Gallium arsenate exhibits the highest value of birefringence in the α-quartz group with Δn=0.033. The transmission in the spectral region above 250nm yields a bandgap of 5.85eV. Piezoelectric properties were measured on resonators. An electromechanical coupling coefficient of 20% was measured which is the highest in the α-quartz group. A quality factor QF of 3.2×1010 was obtained on a Y-cut plate. The C66 elastic constant was found to be 20GPa.

Microporous AlPO4-54 center dot xH(2)O, which exhibits the largest pores among zeolites and aluminophosphates with a diameter of 12.7 angstrom, was investigated at high pressure by X-ray powder diffraction and Raman spectroscopy in diamond anvil cells. The material was found to begin to amorphize near 2 GPa using either a nonpenetrating pressure transmitting medium (PTM) silicone oil or no PTM. When H2O is used as a PTM, amorphization begins at a lower pressure of 0.9 GPa. In this case, superhydration effects are observed and higher relative unit cell volumes are observed prior to the beginning of pressure-induced amorphization (PIA) as compared to the experiment in silicone oil due to insertion of the H2O molecules in the pores. In all cases, in these experiments at room temperature, amorphization was irreversible. Ex situ experiments were used to investigate the local structure of pressure-amorphized AlPO4-54 center dot xH(2)O by nuclear magnetic resonance and by X-ray absorption spectroscopy, which show that, upon increasing pressure, two water molecules enter in the coordination sphere of thereby increasing the coordination number from 4 to 6, which destabilizes the structure. The present results show that the insertion of and/or reaction with guest species can be used to strongly modify the stability of microporous materials with respect to PIA.

Relaxor ferroelectric perovskites are highly polarizable and can exhibit giant coupling between elastic strain and an applied electric field. Here, we report an in situ extended X-ray absorption fine structure (EXAFS) study of a PbZn1/3Nb2/3O3 (PZN) single crystal as a function of the electric field. We show that the strong dipoles in the NbO6 octahedra bonds are aligned along the four < 011 > directions close to the orientation of the electric field, while a small reversible polar shift occurs for Zn in the direction of the electric field, i.e., positive or negative. This reversible Zn-O polar shift is proposed to play an important role in both the "easy" switching of the ferroelectric polarization and the giant piezoelectric effect in PZN.

Confined H2O molecules act as local probes for depressurization phenomena during the pressure induced amorphisation of faujasite NaX at which the OH stretching frequency first decreases and then increases almost to its room pressure value upon further compression. Pair distribution function (PDF) analysis provides evidence that amorphisation corresponds to a collapse of the structure around hydrated sodium cations with strong distortion of the secondary building units (double six-membered rings, sodalite cages). Both the use of guest molecules as local probes in far- and mid-infrared spectroscopy, where we correlate intermolecular water H bonding vibrations and internal mode behaviour under confinement, and PDF analysis could be of great use to study the mechanical behaviour of other hydrated materials.